Diels-alder adducts of hexahalo-cyclopentadiene with quinones



Patented Feb. 5, 1 952 DIELS-ALDER ADDUCTS OF HEXAHALO- CYCLOPENTADIENE WITH QUINONES Rex E. Lidov, Julius Hyman, and Edward Segel,

Denver, 0010.; said Lidov and said Segel assignors to Velsicol Corporation, Chicago, 111., a corporation of Illinois No Drawing.

16 Claims.

Application December 27, 1947, Serial No. 794,204

ates to produce other valuable materials which may have a diversity of uses.

More specifically, this invention is concerned with the reaction of hexahalocyclopentadiene such as hexachlorocyclopentadiene, hexabromocyclopentadiene, or a hexa-chlorobromocyclopentadiene, with quinone such as benzoquinone. naphthoquinone, phenylbenzoquinone, p-thymoquinone, 2,6-dimethyl-1,4-berizoquinone, 2,6-dimethyl-1,4-naphthoquinone, chlorobenzoquinone,

2,3-dichlorobenzoquinone, etc. and with quinone adducts such as the butadiene adduct of hemequinone, the isoprene adduct of benzoquinone,

The reaction herein involved is thought to be a Diels-Alder reaction and may be represented by the following reaction of benzoquinone with hexachlorocyclopentadiene as exemplary of the general reaction herein disclosed.

o 01 H c1 01 01 H H C H:

'01- -01' 01 n B o1 -11 Hexaclilorocyclo- Benzoquinone pentadie'ne Similarly, and again in an exemplary fashion, hexabromocyclopentadiene will react with naphthoquinone in the following manner.

0 o I H Br H H Br Br H B l x Br- -Br I Br H Br I H Br H H The hexachlorocyclopentadiene utilized in the process of this invention may be prepared by any desired method and may be satisfactorily prepared by the following procedure: 7

To 15 liters of approximately 2 molar sodium hypochlorite solution (cooled to about 10 0.), which is also approximately 0.5 molar withrespect to excess sodium hydroxide, is added in one operation an emulsion of 3'76 grams (5.7 moles) freshly distilled cyclopentadiene in 400 ml. water containing 0.2% of 50% technical sodium lauryl sulfate as the emulsifying agent, vigorous mechanical stirring being maintained all the while. No external cooling is required to control the moderately exothermic reaction, the. temperature of the reaction mixture reachinga peak of about 45 C. The reaction mixture consists of two phases, an aqueous phase and a nonaqueous phase. Adequate agitation is therefore required to provide intimate contact'between the two phases, the agitation is continued for a total of two hours after the addition of the cyclopentadiene emulsion. After the stirring has been discontinued, the reaction mixture is allowed to stand long enough to efi'ect a good separation of the aqueous and non-aqueous layer. The nonaqueous layer which contains the hexachlorocyclopentadiene is drawn off and dried over magnesium sulfate. This crude liquid is purified by fractionation through an insulated eight inch Hempel column packed with Berlsaddles; hexachlorocyclopentadiene is collected at a boiling range of 58 C.-64 C. at 1.3 to 1.5 mm. mercury. The once fractionated hexachlorocyclopentadiene thus obtained is carefully refractionated using a Todd fractionating assembly and the fraction boiling between 60-62 C. at 1.4 mm. marcury is collected for use.

Analogously, hexabromocyclopentadiene may be prepared by reacting cyclopentadiene with sodium hypobromite. Hexabromocyclopentadiene reacts with quinones although not :quite as readily as does hexachlorocyclopentadiene.

One of the hexa-heterohalocyclopentadienes,

which may be used as a generator for the newcompositions of matter hereindisclosed, can be prepared as follows:

A solution of 21.1 grams (0.32 mol) of cyclopentadiene, dissolved in 63 ml. of hexane, is added at one time to a vigorously stirred, mixed solution of sodium hypobromite and sodium hypochlorite maintained at 35 C. (The hypo halite solution consists of 0.64 mole of sodium hypobromite and 1.92'moles of sodium hypochlorite prepared from 2.9 molar solutions ofjeac l i of the components; it contains an excess of alkali corresponding to 0.5 molar sodium hydroxide.) The temperature after the addition of cyclopentadiene rises rapidly to 45 C. and is then maintained at, 493 C.-45 C. for one hour. At the end.'of-..this time, agitation is discontinued. and the heavy organic phase is separated, after the addition of approximately 1 volumes (based on the non-aqueous phase) of, hexane to insure good separation from the aqueousphase. After decolorization of the separated organic phase with a decolorizing carbon, the hexane is re rr 1 ove ;l in vacuo. There results 106 grams; oi crude;

ch10ropentabromocyclopentadiene. which may: be purified by conventional means.

The quinones and quinone adducts which are, utilized in this invention may be obtained from commercial sources or prepared according to methods well known in the art. The quinone ad- I ducts may also be obtained by the processes herein described.

' EXAMELE 1 Reaction of. herachlorocyclopentadiene with benzoquinone' (without solvent) I-Iexachlorocyclopentadienev (214, grams); was placed. in a fiask with 82.6. grams benzoquinone and. heated slowly to, a temperature, of, about 130 C.-160 C. and maintained in that temperature range for about fifteen minutes. The. hot mixture Wasthen poured into a chilled beaker and the reaction mixture, after a few, minutes, was quenched withhexane. Multiple recrystallizations from a benzene-hexane mixture resulted. in a yield of a yellow crystalline material melting at 184 C.

Per cent Per cent Per cent H Cl Calculated for Diels-Alder addition I product 34. 53 1.05 55. 85, Foundfor Productof above Example. 34. 71 1. 07 1 55. 60

Thus, the product is the expected adduct of hexachlorocyclopentadiene andbenzoquinone.

. EK ME Reaction of hexachlorocyclopentadienewith benzoqninone (utilizing a solvent) Benzoquinone (54 grams) wasdissolvedin 62 ei-Xy n br h to; fillsie peret s- Hexachlorocyclopentadiene, (133 grams) was added over a forty minute period andrefluxing was continued for about fifteenf minutes. Sol vent .was, removed from the reaction mixture by distillation and the residue was recrystallized. from a benzene-hexane mixture resulting. in a yellow crystalline material melting at v 183? C.- 186 C. A mixture of this product with the prodrnot of Example I melted'without showing depression of the melting point of the, mixture; from that of its components and, therefore, theiproduct is the mono-adduct of hexachlorocyclopentadiene and benzoquinone.

EXAMPLE 11:

Reaction. of hexachlorocyclopentadiene and toluquz'none Toluquinone (1.2 grams) was heated withhexachloroeyclopentadiene (2;? grams) at 130 C. for thirty minutes. On cooling, the solid mass was triturated with hexane, andfiltered The solid light-tan powder,- thus obtained; melted at 163 C;166C; and weighed-3.4'grams; The

EXAMPLE IV Reqction, of, hegggchlorocyclopentadiene with nqphthoquinone Naphthoquinone (8.9 grams) was heated at 13.0? C- 1913- fQui hours intermixed with hexachlorocyclopentadiene (15.6 grams). The reaction mixture was poured into a beaker and the material was triturated with hexane, cooled and filtered. The solid was dissolved in hexanebenzene treated" with charcoal and subsequently recrystallizedfrom hexa-benzene' mixture. The thus purified product weighed-13 grams and meltedyat 1'18 Chg-" C:

Percent Per cent Per cent l H: Q

thee i- Theoretical or Adduct, of Hexach101tocyclopentadiene+Naphthoquinone J. Analysis oLProduct. "l. l. f

Thus the product. is. the Diels A lder. adduct of hexachlorocyclopentadicne. andv naphthoquinone.

Reaction-10f. hexaohlorocyclopentadiene. with phenyl; benzoquinone.

P nvl finz u m ran. an hexachlorocyclopentadiene (8.1 grains) were inter,- mixed and. heated, at 1 30 C, for two hours. The mixture was thenlpou l d} H1170. hexane, filtered, treated with charcoal, and. subsequently recrystallized, from, hexane benzene, mixture.

The thus obtained,adductnieltedat,,167,." C,,-j

It is,understood the examples hereinbefore listed arenot intended to limit the invention but are includedlto disclose the process of the i vention in a more understandable manner, Neges sarily, all. techniques and variations for themanuifacture of the products of this invention have not been included and various modifica tions thereof will be suggested to those skilledin be represented by, thereactionz.

Where X is either chlorine.- q g-broming, R1,

and R2 are either hydrogen atoms, halogen atoms or; any r anic,- ra iqal .o Zen; liphati alicyclic; or aaromaticg natimewhiohzmay: or may. notlhave; a common .bondzasi represented by the; dotted line; hand-b areibonds cioined in .general,, toeach other: but. capable, when R1 and R2 are organic .radijcals havingsa vcommon bond: as: rep.-. resented by V the dotted line, oi 'being joined to hydrogen atoms, halogen atoms," or: organic radicals-as definedabove-and- R3 and- R; are

Generally, the processlherein, conc rned: a

atom-so either hydrogen atoms, halogen atoms or organic radicals as defined above. More simply and concisely, the general reaction can be stated as a Diels-Alder type synthesis in which a hexahalocyclopentadiene acts as the diene and a quinoid compound acts as a dienophile. A quinoid compound is here defined as one having two ketonic oxygen atoms and at least one double bond conjugated with at least one of the ketonic oxygens in a cyclohexane ring. As the term is'here defined, 1,4-benzoquinone, 1,2-benzoquinone, 3-chloro-1,2-naphthoquinone, the butadiene adduct of 1,4-benzoquinone, the hexachlorocyclopentadiene adduct, of 1,4-benzoquinone, etc. are all typical examples of quinoid compounds.

The reaction will not proceed with equal facility in each specific instance and, consequently, the reaction conditions must be varied within the limits hereinbefore listed.

The adducts of quinones with hexahalocyclopentadienes have been found to be very useful in the control of insects such as the common housefly, the German and American cockroach, mosquito larvae, adult squash bug, Colorado potato beetle and various other insects. ferent types of bacteria and fungi may also be controlled by use of the aforementioned adduots.

The new insecticidal compounds of this invention may be utilized in the form of oil sprays, dusts, aqueous emulsions, aerosols, etc., either alone or in association with any other desired toxicants, in preparations and by methods of application known to the art.

We claim as our invention:

1. A new composition of matter comprising the Diels-Alder adduct of a hexahalocyclopentadiene wherein the halogen substituents are of the group consisting of chlorine, bromine and mixtures thereof, as the diene, and a quinone compound of the group consisting of hemequinones and napthoquinones, as the dienophile.

2. A new composition 'of matter comprising the Diels-Alder adduct of a hexahalocyclopentadiene, as a diene, and a quinone as a dienophile, having the general formula X Ra I X i R1 I I X R wherein X is a halogen chosen from the group chlorine and bromine; and R1, R2 and R3 are chosen from the group hydrogen, halogen and hydrocarbon radicals.

l 3. A new composition of matter comprising the Diels-Alder adduct of a hexahalocyclopentadiene, as a diene, and a quinone, as a dienophile, having the general formula X B5] x i? R1 x l it:

wherein X is a halogen-chosen from the group chlorine and bromine; R1 and R2 are hydrocarbon radicals and R3 is chosen from the group hydrogen, halogen hydrocarbon radicals.

Many dif- ,duct, as the dienophile, having the general forwherein R1 and R2 are hydrocarbon radicalsand are derived from a diene reacting with a benzoquinone in the Diels-Alder reaction, R3, R4, and R5 are chosen from the group hydrogen, halogen and hydrocarbon radicals and wherein X is of the group consisting of chlorine, bromine and mixtures thereof.

5. A composition according to claim 1 wherein the hexahalocyclopentadiene is hexachlorocyclopentadiene.

6. A composition according to claim 1 wherein the quinone compound is benzoquinone.

7. The method of forming the addition reaction product of a hexahalocyclopentadiene wherein the halogen substituents are of the group consisting of chlorine, bromine and mixtures thereof and a quinone of the group consisting of benzoquinones and naphthoquinones which comprises reacting a mixture of said constitutents at a temperature of about C.-225 C.

8. The method of forming the addition reaction product of hexachlorocyclopentadiene and a quinone of the group consisting of benzoquinones and naphthoquinones which comprises reacting said constituents at a temperature of about C.-1'70 C.

9. The method of forming the Diels-Alder addition reaction product of hexachlorocyclopentadiene and benzoquinone which comprises reacting said constituents at a temperature of about 130 C.- C.

10. The compound represented by the formula Cl 0 O H t ClC C CH consisting of benzoquinones and naphthoquinones. said adduct having the general formula wherein the letters X represent halogen atoms of the group consisting of chlorine and bromine, and R1, R2, R3 and R4 are selected from the group 7. oonsisting: of; hydrogen,v hadogen anad hydrocarbon'radieals. D

13.v A new composition of matter comprising the- Diels-Alder. adduct of hexachlorocyclopentadime and naphthoquinone.

14. A new composition of matter comprising the Diels-Alder adduct of hexachlorocyclopentadiene and 2,6-dimethy1-1,-naphthoquinone.

15. A new composition of matter comprising the Dials-Alder adduct of hexachlorocyclopentadiene and chlorobenzoquinone.

16. A new composition of matter comprising the DlelseAlden adduct. 01 hexachlorocyelopentm diene and 2,3-dich1orobenzoquinone.

file of this patent:

REX .E. Lmov. JULIUS EDWARD sEGELr. 

1. A NEW COMPOSITION OF MATTER COMPRISING THE DIELS-ALDER ADDUCT OF A HEXAHALOCYCLOPENTADIENE WHEREIN THE HALOGEN SUBSTITUENTS ARE OF THE GROUP CONSISTING OF CHLORINE, BROMINE AND MIXTURES THEREOF, AS THE DIENE, AND A QUINONE COMPOUND OF THE GROUP CONSISTING OF BENZOQUINONES AND NAPTHOQUINONES, AS THE DIENOPHILE. 